Process of producing hydrocarbon materials



- msuLqrm Sept 11, E923; L467f75$ D. T. DAY

PROCESS PRODUCING HYDROCARBON MATERIALS Filed Aug. 22 1919 on. /2 v TO OONPE'NSEE Wee- ,sr-air @FFHQE.

DAVID '1. DAY, OE WASHINGTON, DISTRICT OF COLUMBIA.

PROCESS OF PRODUCING HYDROCARBON MATERIALS.

Application filed August 22, 1919. Serial Ito. 319,179.

To all whom it may concern Be it known that 1, DAVID T. DAY, a citizen of the United States, residing at Washington, District of Columbia, have invented certain new and useful Improvements in Processes .of Producing Hydrocarbon Materials, of which the following is a specification.

This invention relates to the treatment of hydrocarbon oils to produce hydrocarbon oils having low boiling points from hydrocarbon oils having high boilin points.

It is a well recognized fact that heavy oils andv tars are easily broken up by heat, and

it is equally well known that rocesses for performing this function are 0 ten not commercially successful because no dependable.

scheme for removing the carbon formations has been used. One of the chief difiiculties has been that carbon depositions eithereventually choke up the treatment chamber or interfere with the application of heat to the material to be cracked, or in some other way interfere with the operation of the appara-' tus being used.

The resent invention provides for the success ul heat treatment of the oil and a method of continuously disposing of all deposits of coke and carbon. The invention provides for the addition of the fresh heavy hydrocarbon oil or tar to oil bearing shale and the continuous introduction into and removal from a heated retort. During this treatment the oil added and the oil vaporized from the body of the shale passes oil as vapor and gas and the remaining earthy shale content is discharged along with the carbon deposited from the oil so'added. The invention provides for the use of a retort having either gravity or screw conveyor means.

' The fresh oil or tar to be treated is added to or mixed with the oil shale before the shale reaches the retort or while it is in the retort hopper. The shale and .added oil is passed through the retort by a screw conveyor.

.During this passa e the heat on the retort walls causes the s ale to give up its oil by distillation, destructive distillation, and by cracking. The added fresh oil is also partly distilled and cracked'by the action of the hot vapors, which, coming from the retort traverse the shale and the added oilwhile still in the hopper,'so that part of the added heavy oil is actually cracked to lighter products while still in the hopper. This action is undoubtedly facilitated by the catalytic action of the shale, and the continuous process for addition of heavy oils to finely porous bodies in non-caking condition for this cracking purpose by passing the mixture through a retort and the particular way in which this is effected is a discovery for which patent isclaimed. The heavy oil during distillation, destructive and otherwise from the shale gives off light oil vapors and gases and leaves coke deposits within the pores of and attached to the lumps of shales, which latter are continuously discharged as soon as the oil is sufliciently extracted.

The point'of introduction of the heavy fresh 011 or tar into the apparatus may be changed by injecting the fresh material into one of the hot parts of the retort so that the added material will be more quickly cracked than if the oil were added to the shale in the hopper, and with the result that any distillation of the material must necessarily take place under a cracking condition whereas if the oil were added to the shale while in the hopper distillation might take place to a mild degree without the distilled products being directly subjected to cracking temperature.

In the accompanying drawing there is illustrated one form of apparatus which may be used for conducting the process ofany suitable means, not shown. 2 is a main hopper below the receiving hopper 1 and constitutes a mixing chamber. Immediately below the hopper 1 and between the latter and the hop er 2 is a measuring valve 3, the chief functions of which are to provide a measured quantity of shale for the apparatus and to do this in such a manner as not to permit the upward escape of vapors or gases; The valve 3 includes a' plunger 3 having conical upper and lower ends and mounted in the mixin chamber 2. A valve rod 3 extends upwar ly through the receiv ing hopper l and is actuated by mechanism which will be described. The valve rod 3 is attached to a lever arm' 3 which is pivoted at 3. A weight 3 is adjustably mounted on The end of the lever 3 to the valve rod 3" is provided with a roller 3 adapted to bear on a cam wheel 3*. When sutiicient shale has enteredthe hopper 1 to overbalance the weight 3, the plunger 3 starts downward, the cam wheel 3 by mechopposite 'anism not illustrated in the present applicamitting the fresh shale to cover the entrance to the retort and closing the uppefend of.

the chamber 2 by the upper conical end of the plunger. It will be observed from the drawin that at no time in the course of rotation oes the valve provide a direct passage from the hopper 2 to the atmosphere.

At the bottom of the retort is a rotary valve 4 adapted to permit the discharge of spent shale but'to prevent the escape of gases. Positioned beneath the hopper 2 is a furnace casing 5 providing an interior chamber 6 within which are three retort tubes 7.- 8 and 9, res ctively, extending horizontally and one a ve the other. A single tube would serve to amply describe the invention since the number,'size or design of the retort tubes 5 form no part of the present invention. The

process'thus provides for the application of the full force of heat to the material, suflicient toefiect cracking, as soon as it enters the retort. This is because the retort tube is positioned in the furnace and the heat of the latter has free lay about the retort tube to heat the same. The oil material added to the shale is thus substantiall instantaneously volatilized along with w atever material maybe driven off from the interior of the oil shale, and the coke, formed is left on the shale and passed out "of the retort tube with the shale. This heat treatment pre scribed as part of the present invention is to be differentiated from the heat treatment in such rocesses as are directed to simple distillation and do not desire to effect cracking, and which contrasted to the present method provide relatively nioderate temperature or pro 1 ive temperatures to effect fractional distlllation of the crude oil which may be treated or the extraction of the oil content of shale without the cracking of such oil.

. In each retort tube is a screw conveyor and the scope of the invention. The intr of the oil to be treated into the apparatus is in the lowermost artof the furnace .5 there is a bu rn er 10 a opted to burn gaseous or llqllld fuel. Arrangement may be made for the use of solid fuel without departin from uction provided for by a ipe 11 leading into the top of the hopper 2. P p p g 12 the heavy oil is spread over the shale an y means of the perforated trickles down to permeate tne== mass. .The oil shale 'is enriched by the addicould .not combine. It has been found as result of the present invention and related work that such a porous bod as shale acts favorably to romote the combination of the cracked oil withthe hydrogen and hydrogenbearing gases present in the retort with constant benefit to the crackedoils.

When the oil treated shale is passed downward through the valve 3 it is passed to the right by the screw conveyor 7* to the end of the tube 7 where it is dropped over into the tube 8 and there carried to the left by the conveyor 8". At the end of the tube 8 the shale is dropped down into the tube 9 and carried to the end of that tube by the conveyor 9' where it is dumped into the space 13 to be used directly as' fuel, in which case the coke adhering to the shale is consumed, or treated with steam for the production of gas. The apparatus is so timed that in the passage through the retort tubes substantia the shale has been driven off either as vaporized or cracked vapors, and permanent gases. The coke formation ordinarily so troublesome is carried away by the lumps of shale, which thus keep the retort clean and scour the interior thereof and the conveyor screw.

The vapors and gases driven off during passage through the. retorts may be led from the apparatus through a pipe 14 and suitab lly condensed and trapped.

he process may be operated at a slight negative pressure or at a positive pressure up to two hundred pounds in the apparatus described. Variations in the pressures used may be made without departing from the scope of the invention. The temperatures used may vary from 500 F. to 1400 F. according to the results desired. The apparatus has been operated advanta ously on California shale and added F. and above.

has been added in practical operation of the process has had substantially no gasolene present but has yielded excellent amounts of this material when used in accordance with the details of the present procem. Heretofore such material has been not easily used because of the choking up of the apparatus.

hereinbefore mentioned.

alifornia oil at temperatures ran ingfrom 700 F. to 1200 uch of the material which 1y all of the oil present in or added to It is' to be noted particularly that this1 process 1s operated by heat applied to the of shale containing similar volatilizable material. It will be clear that there can be no coke formation within the retort tubes. and hence the heat conductance is never destroyed.

Stress has been laid in this process on the efliciency of shales which bear oil, or incisture, or both, as is usually the case. There I are many other substances, however, such bodies,

v 1. The

as naturally porous rockssuch as sandstones, or rocks which can be made porous by heat, such as lime'stones, which can in a commercially eiiicient degree be used in the place of shale. Further, such organic substances as sawdust and similar porous have also merit for this application, and must be availed of in the proper industrial application of this process where su perior porous bodies cannot be obtained economically. There are many districts in the United States where there is urgent need of this eflicient method of cracking heavy oils, but where oil shales, or shales merely containing moisture, do not exist in industrially economic conditions. In such cases the process must be operated with the best porous material available.

What we claim is:

process of converting hydrocarbon oils having high boiling points to hydrocarbon oils having low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises adding the oil to be treated to a mass of hydrocarbon oil hearing shale adapted to form with the nonvolatile residuum of the oil a dry non-cak ing mixture, continuously introducing the shale with vthe added oil into a retort, subjecting said material while in said retort to cracking temperatures, utilizing the shale while within said retort as a scouring me 'dium for keeping the interior of the retort free from deposits, continuously passing from said retort,

said material so treated and condensing, thus driven olf.

2. The process of converting hydrocarbon oils having high boiling points to hydrocarbon .oils having low boiling points and the low boiling point oils preventing carbon despositions on the interior of the treatment apparatus, whichyprocess comprises addingthe hydrocarbon oil material to be treated to a mass of natural noncaking neutral material, passing the material with the added oil through a retort located in a furnace and heated thereby, subjecting said material and added oil in the v bon oils having high boiling retort to a requisite degree of heat sufficient to drive off all volatilizable material and crack at least a portion of it and leave coke on the neutral material, utilizing the new tral material while within said retort as a scouring medium for keeping the retort free from deposits, and condensing the low boiling pointoils driven off,

3. The process of converting hydrocarbon oils having high boiling points to hydrocarbon oils having low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises adding the oil to betreated to a mass of hydrocarbon oil bearing shale, pass ing the shale with the added oil through a conveyor retort located in a furnace and heated uniformly thereby, subjecting said material while in said retort to cracking temperatures by subjecting the added oil as soon as it enters the retort to the requisite degree of heat sufficient to drive off all volatilizable material and crack a substantial portion and leave coke on the shale, utilizing the shale while within said retort as a scouring medium for keeping the interior of the retort free from deposits, continuously passing the resultant oil vapors'and gas from said retort, continuously passing from the retort the shale and coke formed during the retorting, and condensing the low boiling point oils thus passed from said retort.

4E. The process of converting hydrocarpoints to hydrocarbon oils having low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises adding the oil to be treated to a mass of hydrocarbon oil bearing shale, passing the shale with the added oil through a conveyor retort located'in a furnace and heated uniformly thereby, subjecting said material while in said retort to a heat treatment involving a temperature of at least 700 F. initially applied with the requisite degree sufficient to driveoil all volatilizable material and crack a substantial portion and leave coke on the shale, utilizing the shale while within said retort as a scouring medium for keeping the interior of the retort free from deposits, continuously passing said material so treated from said retort, and condensing the low boiling point oils driven off from the retort.

5. The process of converting hydrocarbon oils having high boiling points to hydrocarbon .oils having'low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises adding the oil to be treated to natural oil bearing earthy material containing volatilizable material, pass ing the earthy material with the added oil through a conveyor retort located in a furnace and heated uniformly thereby, suba heat treatment involving a temperature of at least 700 F. initially applied with the requisite degree suflicient to drive off all volatilizable material and crack a substantial portion and leave cokevon the earthymateria]. utilizing the earthy material while within said retort as a scouring medium for keeping the interior of the retort free from deposits, continuously passing said material so treated from said retort, and condensing the low boiling point oils thus driven off.

6. The process of converting hydrocarbon oils having high boiling points to hydrocarbon oils having low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises adding the oil to be treated natural oil bearing earthy material containing volatilizable material and water, passing the earthy material with the added oil through a conveyor retort located in the furnace and heated uniformly thereby, subjecting said material while in said retort to a heat treatment involving a temperature of at least 700 F. initially applied with the requisite degree suiiicient to drive ofl all of the treatment apparatus, which process comprises adding the hydrocarbon oil to be treated to a mass of solid lumps of natural material containing moisture continuously passing the material with t e added oil through and out of a retort located in a furmace and heated uniformly thereby, subjectdrocarbon oils having low boiling points process comprises addin and preventing carbon depositions on the interior of the treatment apparatus, which the hydrocarbon oil material to be treate to-a mass of natural non-eaking rocky material, passing the material with the added oil through a conveyor retort located-in a furnace and heated uniformly thereby, and subjecting said material and oil while in said retort to a heat treatment of at least 700 F. applied uniformly as soon as the material enters the retort to drive off all volatilizable material and crack at least a portion of it and leave the coke on the rocky material, utilizing the rocky material while within said retort as a scouring medium for keeping the interior of the retort free from deposits, and recover- 1n the low boiling point oils thus driven off by condensing the same.

9. The process of converting hydrocarbon oils having high boiling points to hydrocarbon oils having low boiling points and preventing carbon depositions on the interior of the treatment apparatus, which process comprises subjectin a mixture of hydrocarbon oil material an a mass of natural non-caking neutral material in a com veyor retort located in a furnace and heated uniformly thereby to a heat treatment of at least 700 F., utilizing the neutral material while within said retort as a scouring medium for keeping the interior of the retort free from deposits, removing the neutral material with the carbon de osited thereon from the retort, and ,condensmg the low boiling point oils thus driven ofl', said heat treatment being applied initially and unforml as soon as the material enters the retort with the requisite degree of temperature to drive of? all volatilizable material and crack at least a portion of it. and leave the coke on the neutral material.

10. The process of producing low boiling hydrocarbon oils from high boiling hydrocarbon oils and preventing carbon depositions'on the interior of the treatment apparatus, which process comprises adding the high boiling oil to be converted to solid material which solid material is free from tar and any material which will become sticky under the action: of the added oil and heat, passing the solid material and added'oil through a screw conveyor retort,

. subjecting such mixture of material while in said retort to a temperature treatment sufficient to crack a substantial portion of the added oil, utilizing the solid material while within said retort as a scouring medium for keeping the interior of the retort free from deposits, and recovering the low boiling point oils thus driven off by condensing the same.

11. The process of producing low boiling hydrocarbon oils from high boiling hydrocarbon oils and preventing carbon depositions on the interior of the treatment appalot ratus, which process comprises adding the high boiling oil to be converted to solid material which solid material is free from memee tar and any material which will become sticky under the action of the added oil and heat, passing the solid material and added oil through a screw conveyor retort, subjecting such mixture of material while in said retort to a temperature treatment of at least 700 F. to volatilize and crack a substantial portion of the added oil, utilizing the solid material while within said retort as a scouring medium for keeping the. interior of 1 the retort free from deposits, withdrawing the aeriform material ahd cracked content so produced, passing the solid material out of the retort, and recovering the low boiling hydrocarbon oils by condensing the aeri- 315 form material thus driven off.

In testimony whereof, I aflix my si nature.

DAVID T. AY. 

